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WO1996001293A1 - Systeme de liants a autodecollement pour produits composites - Google Patents

Systeme de liants a autodecollement pour produits composites Download PDF

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Publication number
WO1996001293A1
WO1996001293A1 PCT/US1995/008333 US9508333W WO9601293A1 WO 1996001293 A1 WO1996001293 A1 WO 1996001293A1 US 9508333 W US9508333 W US 9508333W WO 9601293 A1 WO9601293 A1 WO 9601293A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyether
containing compound
polyisocyanate
compound
mixtures
Prior art date
Application number
PCT/US1995/008333
Other languages
English (en)
Inventor
Gilbert Liddell Nelson
Daniel P. Martone
Original Assignee
The Dow Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to BR9506013A priority Critical patent/BR9506013A/pt
Priority to AU29155/95A priority patent/AU679645B2/en
Priority to KR1019960701106A priority patent/KR960704979A/ko
Priority to JP8503952A priority patent/JPH09502763A/ja
Priority to EP95924769A priority patent/EP0719303A1/fr
Priority to CA002170397A priority patent/CA2170397A1/fr
Publication of WO1996001293A1 publication Critical patent/WO1996001293A1/fr
Priority to NO960868A priority patent/NO960868L/no
Priority to FI960997A priority patent/FI960997A0/fi

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/708—Isocyanates or isothiocyanates containing non-reactive high-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2125/00—Compositions for processes using internal mould release agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers

Definitions

  • This invention relates *-o binders useful in preparing composite products. More particularly, it relates to composite products prepared from comminuted, preferably lignocellulosic, materials.
  • organic polyisocyanates as adhesive binders in preparing board products from comminuted Woodstock, including wood flakes, chips, strands or fibers, is well-known. References to such use include, for example, U.S. Patents Nos. 3,428,592; 3,440,180; 3,557,263; 3,636,199; 3,870,665; 3,919,017; and 3,930,110.
  • the binder resins optionally in the form of a solution or aqueous suspension or emulsion, are applied to or admixed with the particles of cellulosic material, or other types of substrate material capable of forming composite articles, using a tumbler apparatus, blender or other form of agitator. The mixture of particles and binder is then formed into a mat and subjected to heat and pressure using heated platens. The process can be carried out in a batch operation or continuously.
  • the present invention is a self-releasing binder composition prepared by contacting at least (1) a polyisocyanate compound, (2) a compound of one of the following formulae in an amount from about 1 to about 20 parts per 100 parts by weight of the polyisocyanate compound:
  • X is oxygen or sulfur
  • R is hydrocarbyl or hydrocarbyl containing an ether or ester group, and may be cyclic
  • R 1 is R, H, or an acyl, carbamoyl, phosphoryl or sulfonyl group
  • a polyether containing compound with the following provisos: (i) wherein the polyether containing compound contains no active hydrogen, the polyether containing compound is present in an amount from about 1 to about 2000 parts per 100 parts by weight of the polyisocyanate; and (ii) wherein the polyether containing compound contains at least one active hydrogen, the polyether containing compound is present in an amount such that, for compounds of Formula I, the OH:NCO equivalency ratio is less than about 0.77:1.00; for compounds of Formula II, the OH:NCO equivalency ratio is less than about 0.25:1.00; and for compounds of Formula III, the OH:NCO equivalency ratio is less than about 0.10:1.00; under
  • the present invention is a process for preparing a composite article comprising contacting at least (1) a polyisocyanate compound; (2) a compound of one of the following formulae in an amount from about 1 to about 20 parts per 100 parts by weight of the polyisocyanate:
  • the self-releasing binder composition comprising components (1) , (2) and (3) as described hereinabove, allows for excellent binding and maintenance of the internal bond strength of the substrate particles to be compacted to form the composite article.
  • These substrate particles may include inorganic, polymeric, or other organic or, particularly, cellulosic particles such as wood flakes, chips, particles, strands or fibers, or other comminuted substrates.
  • the binder system provides for easy release of the final composite article from aluminum, steel, or other types of metal molds or platens. It thus is ideally suited for uses such as continuous commercial board production lines, where rapid, easy release is sought.
  • the first required component of the self-releasing binder system is a polyisocyanate' (1) .
  • polyisocyanate refers to any isocyanate having an average functionality of 2 or greater, i.e., an average of at least two isocyanate groups per molecule.
  • diisocyanates are encompassed thereby.
  • organic polyisocyanates are diphenyl-methane diisocyanate, m- and p-phenylene diisocyanates, chlorophenylene diisocyanate, ⁇ , ⁇
  • polystyrene resin polystyrene resin
  • triphenylmethane triisocyanates 4, 4 '-diisocyanato-diphenyl ether
  • polymethylene polyphenyl polyisocyanates are mixtures containing from about 25 to about 90 percent by weight of methylenebis (phenyl isocyanate), the remainder of the mixture being polymethylene polyphenyl polyisocyanates of functionality equal to or greater than about 2.0.
  • Such polyisocyanates and methods for their preparation are well-known in the art; see, for example, U.S. Pat. Nos. 2,683,730; 2,950,263; 3,012,008 and 3,097,191.
  • These polyisocyanates are also available in various modified forms.
  • One such form comprises a polymethylene polyphenyl polyisocyanate.
  • polymethylene polyphenyl polyisocyanates are the preferred polyisocyanates for use in the binder systems of the invention.
  • Particularly preferred polymethylene polyphenyl polyisocyanates are those which contain from about 35 to about 65 percent by weight of methylene bis (phenylisocyanate) .
  • the organic polyisocyanate can, in one embodiment of the present invention, be employed in the binder system in the form of an aqueous emulsion or dispersion.
  • the aqueous emulsion or dispersion can be prepared using any of the techniques known in the art for the preparation of such, prior to use of the composition in the binder.
  • the polyisocyanate can be dispersed in water in the presence of an emulsifying agent.
  • the latter can be any of the emulsifying agents known in the art, including anionic and nonionic agents.
  • nonionic emulsifying agents are polyoxyethylene and polyoxy-propylene alcohols and block copolymers of two or more of ethylene oxide, propylene oxide, butylene oxide, and styrene; alkoxylated alkylphenols such as nonylphenoxy poly(ethyleneoxy) ethanols; alkoxylated aliphatic alcohols such as ethoxylated and propoxylated aliphatic alcohols containing from about 4 to 18 carbon atoms; glycerides of saturated and unsaturated fatty acids such as stearic, oleic, and ricinoleic acids; polyoxyalkylene esters of fatty acids such as stearic, lauric, and oleic acids; and fatty acid amides such as the dialkanolamides of fatty acids including, for example, stearic, lauric, and oleic acids.
  • alkoxylated alkylphenols such as nonylphenoxy poly(ethyleneoxy) ethanol
  • the formation of the emulsion or dispersion can be carried out at any time prior to its use with the binder composition. Any of the methods conventional in the art for the preparation of aqueous emulsions can be employed in preparing the aqueous polyisocyanate emulsions, such as the use of an in-line mixer just prior to application of the polyisocyanate to the selected substrate particles.
  • an organic acid compound (2) selected from compounds of the formulae:
  • R and R' are selected from the group consisting of alkyl having at least 3 carbon atoms, alkenyl having at least 3 carbon atoms, aryl, aryl substituted by at least one alkyl, alkyl substituted by from 1 to 2 acyloxy groups wherein the acyl group is the residue of an aliphatic monocarboxylic acid having at least 2 carbon atoms.
  • Each of the groups R and R' in the various formulae set forth above can optionally be substituted by one or more inert substituents, i.e., substituents which do not contain active hydrogen atoms and which are therefore unreactive in the presence of the polyisocyanate.
  • inert substituents are alkoxy, alkylmercapto, alkenyloxy, alkenylmercapto, chloro, bromo, iodo, fluoro, cyano and the like.
  • the compounds therefore comprehended by the above formulae include, for example, acid phosphates, sulfonic acids and carboxylic acids. Also included are the organic acid anhydrides or mixed anhydrides, for example, o-monoacyl, carbamoyl, phosphoryl and sulfonyl derivatives of either group; polyphosphates including branched polyphosphates and cyclometaphosphates; and mixtures thereof.
  • anhydrides includes, in part, pyrophosphates and pyrosulfates derived from the phosphorus-containing compound (I) or the sulfur-containing compound (III) .
  • the pyrophosphates and pyrosulfates are obtained from their respective acid phosphates or acid sulfates by reaction of the latter with a dehydrating agent, such as carbonyl chloride, aryl or alkyl monoisocyanates and polyisocyanates, N,N'-dihydrocarbylcarbodiimides, and the like, in accordance with procedures well-known in the art; see, for example, F. Cramer and M. Winter, Chem. Ber. 94, 989 (1961); F. Ramirez, J.F. Marecek and I. Ugi, J. Am. Chem. Soc. 97, 3809 (1975) .
  • Preferred for the phosphorus- or sulfur-containing compound selection are liquid esters, including monoesters, diesters and combinations thereof, which are well-known, commercially available materials.
  • the acid phosphates of Formula (I) can be readily prepared in the form of mixtures of mono-and-diesters by reaction of an alcohol ROH or thiol RSH, wherein R is as defined above, with phosphorus pentoxide or oxysulfide in accordance with well-established procedures; see, for example, Kosolapoff,
  • Organophosphorus Compounds pp. 220-221, John Wiley and Sons, Inc., New York, 1950. Also preferred are the pyrophosphates or mixed pyrophosphates derived from mixtures of acid phosphates, and the pyrosulfates or mixed pyrosulfates derived from mixtures of sulfonic acids, readily obtained through methods cited above.
  • Illustrative of the phosphorus-containing compounds of Formula (I) above which can be employed individually or in combination with other acid phosphates in the process of the invention are monoester acid phosphates such as mono-O-octyl, mono-O-nonyl and mono-O-decyl acid phosphate; diester phosphates such as 0,0-di (octyl) , 0,0-di (nonyl) and 0,0-di (decyl) acid phosphate; pyrophosphates such as tetraoctyl, tetranonyl and tetradecyl as well as di(octyl), di(nonyl) and di(decyl) pyrophosphates; and polyphosphates terminated with mono-O-octyl, mono-O-nonyl and mono-O-decyl groups, or 0,0-di (octyl) , 0,0-di (nony
  • esterifying radical is that derived from a monohydric alcohol which has been capped using the appropriate molar proportions of ethylene oxide, propylene oxide, epichlorohydrin or 1, 1, 1-trichlorobutylene oxide, are particularly advantageous in the present invention.
  • Additional phosphate compounds which are useful in this invention include monoacyl acid phosphates such as O-decanoyl, O-dodecanoyl and O-benzoyl derivatives, prepared as described by Kosolapoff, ibid, p. 334, and carbamoyl phosphates such as octenylcarbamoyl, decenylcarbamoyl and dodecenylcarbamoyl phosphates, prepared as described by F. Cramer and M. Winter, Chem. Ber., pp. 92, 2761 (1959).
  • monoacyl acid phosphates such as O-decanoyl, O-dodecanoyl and O-benzoyl derivatives, prepared as described by Kosolapoff, ibid, p. 334
  • carbamoyl phosphates such as octenylcarbamoyl, decenylcarbamoyl and dodecen
  • carboxylic and polycarboxylic acids are also useful in the present invention.
  • polycarboxylic acids and polyfunctional carboxylic acids can be formulated to have a low viscosity for convenient spray application, along with the other components of the present invention, to the substrate particles.
  • Particularly suitable sulfonic acids shown by Formula (III) hereinabove include, for example, decane sulfonic acid, octadecane sulfonic acid, benzene sulfonic acid, toluene sulfonic acid, naphthalene sulfonic acid, cyclohexane sulfonic acid, and aromatic monosulfonic acids of the type which may be obtained in known manner by the sulfonation of alkyl benzenes such as hexyl-benzene, dodecyl-benzene, octadecyl-benzene or mixtures thereof.
  • polyether containing compound (3) is also employed.
  • the polyether containing compound can contain an active hydrogen, or can have, as its terminal or pendant groups, moieties that are not active hydrogens and are otherwise unreactive, that is, substantially inert, toward the polyisocyanate.
  • the "polyether containing compound” therefore includes any compound containing one or more polyether moieties, whether or not such would be classified by standard nomenclature as primarily or essentially a polyether compound.
  • the polyether compound contains active hydrogens. Determination of whether there is an active hydrogen can be determined by use of the Zerewitinoff Test, as described in J.B. Niederl and V. Niederl, Micromethods of Quanitative Organic Analysis, p. 263 (New York 1946) .
  • the active hydrogen in such compounds reacts with polyisocyanates to form polyurethanes and related polymers, including polyureas and polyurethane/polyureas, and therefore, in some embodiments of the present invention the result is a polyurethane, polyurea or polyurethane/polyurea polymer binder.
  • the active hydrogen containing compound is preferably a hydroxy-functional compound such as a polyol or monol.
  • any polyether polyol typically employed in the art for preparation of polyurethane and related polymers including so-called polyester polyols which contain polyether moieties (also called polyether polyester polyols), are suitable, and can have hydroxyl numbers which vary over a relatively wide range, preferably from 10, more preferably 100, to 6,000, more preferably to 600.
  • Preferred alcohols include polyols and monols selected from the following classes of compositions, alone or in admixture: (a) alkylene oxide adducts of poly-or-monohydroxy-alkanes or alkenes;
  • alkylene oxide adducts of non-reducing sugars and sugar derivatives (b) alkylene oxide adducts of non-reducing sugars and sugar derivatives; (c) alkylene oxide adducts of phosphorus and polyphosphorus acids; and (d) alkylene oxide adducts of polyphenols.
  • base polyols Polyols of these types are referred to herein as "base polyols”.
  • alkylene oxide adducts of polyhydroxyalkanes useful herein are adducts of ethylene glycol, propylene glycol, 1, 3-dihydroxypropane, 1, 4-dihydroxybutane, and 1, 6-dihydroxyhexane, glycerol, 1,2,4-trihydroxybutane, 1,2, 6-trihydroxyhexane,
  • pol (oxypropylene) glycols are also useful.
  • triols are also useful.
  • tetrols are also useful.
  • hexols are also useful.
  • These polyols also include poly(oxypropyleneoxyethylene)polyols.
  • the ethylene oxide when used, can be incorporated in any way along the polymer chain, for example, as internal blocks, terminal blocks, or randomly distributed blocks, or any combination thereof.
  • polyester polyols and thiol compounds which contain polyether moieties are useful in this invention.
  • polyether containing compounds such as polyamines, amine-terminated polyols, polymercaptans and other isocyanate-reactive compounds are also suitable in the present invention.
  • Another preferred class of polyols includes the "copolymer polyols", which are base polyols containing stably dispersed polymers such as acrylonitrile-styrene copolymers.
  • copolymer polyols which are base polyols containing stably dispersed polymers such as acrylonitrile-styrene copolymers.
  • Other types of polyether polyols useful in the process of the invention include polyurea polyols, such as are disclosed in U.S. Patents 3,325,421; 4,042, 537; 4,089,835; polyoxamate polyols, such as are disclosed in U.S.
  • Patent 4,407,983; and polyisocyanate- polyaddition products such as are disclosed in U.S. Patents 4,374,209; 4,324,716; 4,310,448; 4,310,449; 4,350,857; and 4,305,858.
  • Polyether containing compounds which do not possess active hydrogens are also useful for the practice of this invention.
  • Inert reaction products of the polyether polyols, polyamines or polythiols heretofore described constitute an important group of these compounds.
  • the term "inert” means that the reaction product is substantially unreactive with the polyisocyanate, in accordance with J.B. Niederl and V. Niederl, Micromethods of Quanitative Organic Analysis, p. 263 (New York 1946), in the self-releasing binder composition.
  • inert reaction products may be formed by addition of a polyether compound containing active hydrogens, epoxides or any group reactive with an isocyanate, to a stoichiometric excess of polyisocyanate, forming what are commonly termed as prepolymers, which contain at least one reactive isocyanate functional group.
  • the prepolymer thus formed may contain polyurethane, polyurea, polythiourea, or other moieties implicit in the prior description of the active hydrogen containing compounds.
  • a second group of inert reaction products of polyether polyols are those formed by esterification of the polyether polyol with organic acids or organic acid anhydrides.
  • Polyethers comprising ethylene oxide, propylene oxide, butylene oxide and tetramethylene oxide, copolymers or mixtures thereof, and possessing mono-or-polyhydroxy functionalities may thus be reacted with common acids or acid anhydrides through known procedures to prepare inert polyether esters.
  • common acids are acetic, propionic. lauric, and toluene sulfonic acid, while acetic and phthalic anhydride are illustrative of common anhydrides .
  • a third group of inert polyether containing compounds can be prepared by reaction of a polyether polyol with monoisocyanates to form carbamoyl derivatives.
  • Urea, thiourea, epoxide and siloxane derivatives are likewise available through reaction with corresponding polyether containing amine, thiol, epoxy and siloxane compounds, respectively.
  • An example of a monoisocyanate that can be suitably employed is phenyl isocyanate.
  • polyether containing compounds which are otherwise unreactive toward isocyanates that is, which do not contain any active hydrogen, are tresylate, acrylate, aldehyde and succinimidyl derivatives of polyethylene glycol.
  • unreactive compounds are polyalkoxy ethers, polyalkoxy epoxides, polyalkoxy siloxanes, polyalkoxy amides, and polyalkoxy ketones wherein the pendant or terminal active hydrogens or functional groups have been reacted as hitherto described.
  • the weight ratio between such "inert" polyether containing compound and polyisocyanate be from 1, more preferably from 4, and most preferably from 6, to 2,000, more preferably 20, and most preferably 15, parts per 100 parts of polyisocyanate.
  • the starting materials for a composite article also comprise substrate particles. These particles are, in one preferred embodiment, cellulosic and capable of being compacted and bonded into the form of boards. Typical such materials are wood particles derived from lumber manufacturing waste such as planar shavings, veneer chips, and the like.
  • Particles of other cellulosic material such as shredded paper, pulp or vegetable fibers such as corn stalks, straw, and bagasse, and of non-cellulosic materials such as scrap metals; polyurethane, polyisocyanurate, polyethylene and similar polymers; glass fibers; and combinations thereof, can also be used.
  • Inorganic materials such as hydrated alumina, gypsum, and chopped mineral fibers can be employed, either alone or in combination with any of the above cellulosic or non-cellulosic materials, in the formation of particleboards or other composite articles in accordance with the present invention. If desired, mixtures of various types of cellulosic particles may also be used. If cellulosic particles are selected as the substrate material, it is generally preferred that the starting moisture content thereof is less than about 25 percent by weight.
  • segregated components (1), (2) and (3) may be brought together simultaneously to be applied to the substrate particles.
  • the term "simultaneously” implies the act of bringing together the segregated components (l)-(3) prior to application to the substrate particles, whether it is accomplished through prior combination of (2) and (3) followed by contact with (1), or, the act of bringing together is accomplished in a single stream which is fed by the hitherto segregated components (1), (2), and (3) .
  • the selected organic acid containing compound is pre-blended with an active hydgrogen-containing polyether compound, such as a polyether polyol.
  • an active hydgrogen-containing polyether compound such as a polyether polyol.
  • the weight ratio of the organic acid-containing compound to the active hydrogen containing polyether compound is preferably from 1:7600 to 1:0.10, more preferably from 1:275 to 1:0.70, and most preferably from 1:12 to 1:1.
  • the viscosity of the organic acid-containing compound/active hydrogen polyether containing compound blend be from 10, more preferably 50, to 5,000, more preferably 400, centipoise (cps) .
  • component (2) which are solid or not soluble in the polyether containing compound at room temperature, it is desirable to heat to their melting or solubility point in order to produce a homogeneous blend.
  • the higher monoester forms of liquid acid phosphates such as 2-ethylhexyl- or isodecyl-, due to their greater ease of handling and compatibility with the polyol.
  • the blend is then ready to be contacted with the polyisocyanate and applied to the cellulosic or other type of substrate particles.
  • the weight ratio of the organic acid containing compound to the polyisocyanate be from about 4, preferably from about 6, to about 12 parts, more preferably about 8 parts, organic acid-containing compound, to about 100 parts polyisocyanate. Because the polyisocyanate and active hydrogen polyether containing compound react to form a polyurethane and/or polyurea polymer, it is necessary, when the components are all mixed together prior to application to the particles, that such application occur within a relatively short period of time after mixing.
  • any means, method, equipment or conditions generally known to or used by those skilled in the art of polyurethane and related polymer production may be used. These include, for example, impingement mixing to a spray head; simple mixing, as by hand or mechanical means on either a small or large scale; or by use of rollers or shakers. Since the reaction between the polyisocyanate and the isocyanate-reactive constituent of the blend is exothermic in nature, it is preferred that such contact be carried out at a temperature from 0°C, more preferably 20°C, to 50°C, more preferably 30°C.
  • each of the components of the binder composition can be simultaneously mixed, as, for example, using a three-stream mixhead, without pre-blending of the organic acid compound (2) with the polyether containing compound (3) .
  • the organic acid compound (2) can be pre-blended with the polyisocyanate (1) . In this case it is preferable that such pre-blending be accomplished just prior to contact with the polyether containing compound, since the polyisocyanate and organic acid compound (2) may in some cases be reactive and therefore may not be sufficiently storage-stable.
  • the components of the binder composition, (1), (2) and (3) are combined and processed into a storage-stable material which is stored in a single container, until needed for application to the substrate particles (4) .
  • a storage-stable material which is stored in a single container, until needed for application to the substrate particles (4) .
  • means are available for processing organic acid containing compounds (2) through reaction with polyisocyanates such that reaction products are inert and no longer reactive toward polyisocyanates . Examples of this are found in US 4,258,169, US 4,478,738 and US 4,772,442.
  • the polyether containing compound (3) may be combined with the polyisocyanate (1) in a manner consistent with the presence or absence of active hydrogens in the compound.
  • a prepolymer of an active hydrogen polyether containing compound such as a polyether polyol
  • an inert polyether containing compound such as an esterified polyether monol
  • a polyisocyanate can be blended with a polyisocyanate.
  • the reaction or blending with the polyisocyanate can occur with a polyisocyanate which has already been reacted with the organic acid containing compound (2) , or, may first be reacted with or blended with the polyisocyanate which subsequently undergoes reaction with the organic acid containing compound, or, in cases wherein there is insignificant reactivity between the polyether containing compound (3) and organic acid containing compound (2), they may be added in concert to the polyisocyanate (1) .
  • (1), (2) and (3) are processed into a liquid storage-stable mixture by heating the polyisocyanate (1) at a temperature from about 60°C to about 190°C; combining therewith, either simultaneously or subsequently, from about 1 to about 20 parts, per 100 parts of polyisocyanate, each of (2) and (3) to form a reaction mixture; maintaining the heating for a time such that no phase separation occurs upon cooling the reaction mixture to ambient temperatures .
  • an organic acid is combined with a polyisocyanate over a temperature range from about 60 to about 190°C for two hours; then a polyether containing compound which contains no active hydrogens is added.
  • the organic acid is an acid phosphate; the polyisocyanate is a polymeric isocyanate, and the polyether containing compound is an esterified polyether monol.
  • the organic acid and the polyether containing compound are preferably used in an amount of 1 to 20 parts, based on 100 parts of polyisocyanate. In a still more preferred embodiment, 4-12 parts of acid phosphate and 6-20 parts of polyether containing compound, based on 100 parts of polyisocyanate, are used. It is also more preferred to use a temperature from 60-100°C.
  • the esterified polyether monol can be added at an elevated temperature to react out minor amounts of active hydrogen containing impurities that may be present, in which case it is preferable to perform the addition at 60-80°C, maintaining this temperature for 0.5-1.5 hours until the impurities are rendered inert. In any case, heating is maintained for a time such that substantially no phase separation occurs upon cooling the reaction mixture to ambient. If no active hydrogen containing impurities are present, the esterified polyether monol can be blended with the polyisocyanate containing the reaction product of the acid phosphate, at ambient temperature.
  • This self- releasing binder composition is a liquid, storage-stable material and may be stored for a considerable period of time until desired for application to substrate particles.
  • a polyether polyol (3) and an acid phosphate (2) can be added to a stoichiometric excess of polyisocyanate (1) maintained between 60-100°C for 2 to 3 hours.
  • the same proportions of materials as previously described are employed.
  • the preferred polyisocyanate has a relatively high monomeric methylene bis(phenyl) isocyanate content, such that the viscosity of the final reaction product is preferably from 50 to 1000 cps, more preferably to 500 cps . If desired, a relatively low viscosity product can be blended with a higher order polymeric isocyanate to increase viscosity.
  • a relatively high viscosity product formed from a higher order polymeric isocyanate
  • a polyisocyanate containing a significant proportion of methylene bis(phenyl) isocyanate can be blended with a polyisocyanate containing a significant proportion of methylene bis(phenyl) isocyanate to achieve a lower viscosity product.
  • the amounts of reactants are adjusted accordingly such that the final product falls within the preferred weight ranges.
  • a total of from about 2 to 8 percent by weight of the binder system (total constituent weight, excluding any moisture which may be present in the particles) is added, based on the "oven dry" weight of the particles, but higher or lower amounts of binder system may be used in any given application.
  • the particles are of large size, such as in strand board and wafer board, it is possible to use amounts of binder less than 1 percent by weight, based on the "oven dry" weight of the particles.
  • the particles are very small, that is, have a high surface area to volume ratio as in the case of powdered inorganic materials, it is desirable to use amounts of binder up to about 30 percent by weight, preferably to about 20 percent by weight.
  • other materials such as wax sizing agents, fire retardants, pigments, and combinations thereof, may also be added to the particles before or during the application of the binder system to the substrate particles.
  • the coated substrate particles are concurrently or subsequently formed into a loose mat or felt, preferably containing from 4 percent to 20 percent moisture by weight.
  • the mat is then placed in a heated press and compressed to consolidate the substrate particles into a compact composite article.
  • Pressing times, temperatures and pressures vary widely depending on the thickness of the board produced, the desired density of the board, the size of the particles used, and other factors well known in the art. For example, for 0.5 inch thick particle board of medium density, pressures of from about 300 to about 700 psi and temperatures of from about 325°F to about 400°F are typical. Pressing times are typically from about 2 to about 5 minutes.
  • the above-described process can be carried out on a batch basis, that is, individual sheets of particle board can be molded by treating an appropriate amount of particles with the binder resin combination and heating and pressing the treated material.
  • the process can be carried out in a continuous manner by feeding treated particles in the form of a continuous web or mat through a heating and pressing zone defined by upper and lower continuous belts to which, and through which, the necessary heat and pressure are applied.
  • DOWANOLTM 500 denotes a product available from The Dow Chemical Company which is a 500 molecular weight monol prepared from heterofed ethylene oxide and propylene oxide.
  • P-425 denotes a product available from The Dow Chemical Company which is a 425 molecular weight propylene oxide-based polyether polyol.
  • E-400 denotes a product available from The Dow Chemical Company which is a 400 molecular weight ethylene oxide-based polyether diol.
  • ETHFACTM PD-0 denotes a product available from Ethox Corporation which is a high mono-ester isodecyl acid phosphate.
  • ETHOXTM 101 denotes a product available from Ethox Corporation which is a monoester/diester blend of isodecyl acid phosphate.
  • BIO-SOFTTM S-100 denotes a product available from Stepan Company which is a linear dodecylbenzene sulfonic acid.
  • STEPANTANTM H-100 denotes a product available from Stepan Company which is a branched dodecylbenzene sulfonic acid.
  • PRIPO TM 1009 denotes a product available from Unichema International which is a C ⁇ Q dimer carboxylic acid.
  • MPEG 350 AC denotes a product available from The Dow Chemical Company which is an acetate ester of a 350 molecular weight methoxy polyethylene glycol monol.
  • GLY PO AC denotes a product available from The Dow Chemical Company which is a triacetate ester of a 1800 molecular weight propoxylated glycerin.
  • KESSCOTM PEG 200 DL denotes a product available from Stepan Company which is a dilaurate ester containing four moles of ethylene oxide.
  • PAPITM 27 denotes a product available from the Dow Chemical Company, which is a polymeric diphenylmethane diisocyanate having a 134 isocyanate equivalent weight.
  • PAPITM 88 denotes a product available from The Dow Chemical
  • ISONATETM 125M denotes a product available from The Dow Chemical Company, which is diphenylmethane diisocyanate having a 125 isocyanate equivalent weight Examples 1- 6
  • binder compositions (examples 1-6) of the present invention were prepared using the formulations shown in
  • Controls 1, 3 and 4 Three additional binder compositions (controls 1, 3 and 4) were also prepared and did not contain any polyether containing compounds (3) ; therefore, these do not represent embodiments of the present invention and are included for comparative purposes only.
  • Each formulation was run at a polyisocyanate: polyether:organic acid weight proportion of 100 parts:13.6 parts:9.9 parts, except for controls 1, 3 and 4 which were run at a polyisocyanate:organic acid ratio of 100 parts:9.9 parts.
  • Control 2 contained only polyisocyanate.
  • the polyisocyanate used for each of the examples and controls was PAPITM 88.
  • the organic acid containing compound (2) was blended with the polyether containing compound (3) at room temperature prior to contact with the isocyanate (1) .
  • the polyether containing compound (3) was weighed into a beaker, the organic acid (2) was weighed into the same beaker, and the two compounds were then stirred together for several minutes until a clear, homogenous blend was produced. This blend remained as a single phase for several weeks.
  • composite boards were prepared at 6.2 percent binder content, based upon the dry weight of standard aspen oriented strandboard wood flakes (typically 3 inch by 1 inch by 0.05 inch), in order to test releasability of the formulations.
  • the formulations were metered together and sent through a static mixers just prior to spray application to wood flakes.
  • the wood particles were tumbled in a rotating drum and the spray was introduced at a rate of 1 to 5 grams per second (g/s) through a port in the drum.
  • the spray application lasted for 1 to 3 minutes, and the wood flakes were allowed to tumble an additional 10 minutes.
  • the wood flakes were handlaid together into either a 2 foot by 2 foot or a 10 inch by 10 inch deckle box which was positioned on a steel caul.
  • the wood mat was then pressed with the steel caul on the bottom, using either a steel caul sheet on top or directly against the top press platen.
  • Typical press parameters were employed, using a time of 3 minutes; a temperature of 190°C; and a pressure of 400-500 psi (2.75 MPa - 3.44 MPa).
  • the press surfaces were initially cleaned thoroughly, but the surface was not otherwise treated before or during the press run.
  • release is defined to mean that the part being prepared did not need to be pried from surfaces and did not leave behind particles that had to be scraped from the surface before another part could be pressed thereon.
  • Controls 1-4 are for comparative purposes only and do not represent an embodiment of the present invention.
  • Example 7
  • a 3000 g (80.6 percent by weight) portion of PAPITM 27 was charged into a multinecked reactor equipped with mechanical agitator and nitrogen purge.
  • the polyisocyanate was heated to 80-85°C, whereupon a 300 g (8.1 percent by weight) portion of ETHFACTM 101 was added over about 15 minutes with mild foaming ensuing.
  • 420 g (11.3 percent by weight) of MPEG 350 AC was introduced over a 12 minute time period and the reaction was maintained between 80-85°C for an additional 1.5 hour.
  • a single-phase, homogeneous liquid was obtained.
  • a 3000 g (80.6 percent by weight) portion of PAPITM 27 was heated to 82°C; subsequently, 300 g (8.1 percent by weight) of ETHFACTM 101 was added over a 17 minute period with mechanical agitation and nitrogen purge. Mild foaming ensued.
  • the reaction was maintained for 30 minutes at 82°C, then 420 g (11.3 percent by weight) of GLY-PO AC was added during a 20 minute period. After an additional 1.5 hour at 80-83°C, the reaction mixture was cooled to room temperature, yielding a homogeneous, single-phase liquid.
  • a mixture of 80 g (8.6 percent by weight) of ETHFACTM 101 and 110 g (11.8 percent by weight) DOWANOLTM 500 was introduced into a 243 g (26 percent by weight) portion of ISONATETM 125M which has been heated at 85°C under nitrogen purge. The introduction is carried out over a 45 minute period. The colorless MDI became a golden yellow with foam evident after about 8 minutes into the addition period. The reaction mixture was maintained at 81-89°C for an additional 1.75 hour, then allowed to cool, revealing a turbid yellow, somewhat viscous consistency. The mixture was then blended with 500 g (53.6%) of PAPITM 88 at ambient temperature.
  • Control 5 The comparative examples designated as controls 5, 6 and 7 are for comparative purposes only, and are not considered to represent embodiments of the present invention. Comparative Example: Control 5
  • ETHFACTM 101 A 15.1 g (7 percent by weight) amount of ETHFACTM 101 was added to 200 g of PAPITM 88, heated to 90°C under nitrogen, during a 10 minute interval. The reaction was continued at 90°C for an additional 2 hours.
  • Examples 7, 8, and 10 and controls 5 and 6 were performed using pine wood.
  • Examples 9 and control 7 were performed using aspen wood.
  • Controls 5-7 are for comparative purposes only and do not represent an embodiment of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition destinée à une composition liante à autodécollement utile pour préparer un article composite préparé par mise en contact d'au moins (1) un composé polyisocyanate, (2) un composé d'une des formules (I), (II), (III), en une quantité allant d'environ 1 à environ 20 parties pour 100 parties en poids du composé polyisocyanate, formules dans lesquelles X représente oxygène ou soufre, R représente hydrocarbyle ou hydrocarbyle contenant un groupe éther ou ester, et peut être cyclique, et R' représente R, H ou un groupe acyle, carbamoyle, phosphoryle ou sulfonyle, et (3) un composé contenant un polyéther au conditions suivantes: (i) le composé contenant le polyéther ne contient aucun hydrogène actif, le composé contenant le polyéther est présent en une quantité comprise entre environ 1 et environ 2000 parties pour 100 parties en poids de polyisocyanate; et (ii) le composé contenant le polyéther contient au moins un hydrogène actif, ledit composé contenant le polyéther est présent en une quantité telle que, pour des composés de la formule (I), le rapport d'équivalence OH:NCO est inférieur à environ 0,77:1,00; pour des composés de la formule (II), le rapport d'équivalence OH:NCO est inférieur à environ 0,25:1,00; et pour des composés de la formule (III), le rapport d'équivalence OH:NCO est inférieur à environ 0,10:1,00; dans des conditions de réaction suffisantes pour former une composition de liant. Les composants constituant la composition de liant à autodécollement peuvent être appliquées sur des particules de substrat, lesquelles peuvent être, par exemple, des particules cellulosiques, polymères, inorganiques ou similaires, ou bien des combinaisons de celles-ci. Cette combinaison permet une excellente adhésion des particules tout en offrant une aptitude au décollement depuis une large variété de surfaces métalliques avec facilité et de manière fiable.
PCT/US1995/008333 1994-07-05 1995-06-30 Systeme de liants a autodecollement pour produits composites WO1996001293A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
BR9506013A BR9506013A (pt) 1994-07-05 1995-06-30 Sistema aglutinante de autoliberação para produtos compósitos
AU29155/95A AU679645B2 (en) 1994-07-05 1995-06-30 Self-releasing binder system for composite products
KR1019960701106A KR960704979A (ko) 1994-07-05 1995-06-30 복합 제품용 자기 이형 결합제 시스템(Self-releasing binder system for composite products)
JP8503952A JPH09502763A (ja) 1994-07-05 1995-06-30 複合製品用自己離型性接着剤
EP95924769A EP0719303A1 (fr) 1994-07-05 1995-06-30 Systeme de liants a autodecollement pour produits composites
CA002170397A CA2170397A1 (fr) 1994-07-05 1995-06-30 Systeme de liants a autodecollement pour produits composites
NO960868A NO960868L (no) 1994-07-05 1996-03-04 Selv-frigjörende bindesystem for kompositt-produkter
FI960997A FI960997A0 (fi) 1994-07-05 1996-03-04 Itsestään irtoava sideainesysteemi yhdistelmätuotteille

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US27094494A 1994-07-05 1994-07-05
US08/270,944 1994-07-05
US33316694A 1994-10-02 1994-10-02
US08/333,166 1994-10-02

Publications (1)

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WO1996001293A1 true WO1996001293A1 (fr) 1996-01-18

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EP (1) EP0719303A1 (fr)
JP (1) JPH09502763A (fr)
KR (1) KR960704979A (fr)
CN (1) CN1131958A (fr)
AU (1) AU679645B2 (fr)
BR (1) BR9506013A (fr)
CA (1) CA2170397A1 (fr)
FI (1) FI960997A0 (fr)
MY (1) MY130593A (fr)
NO (1) NO960868L (fr)
WO (1) WO1996001293A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998056843A1 (fr) * 1997-06-09 1998-12-17 Basf Aktiengesellschaft Emulsifiants
JP2012251063A (ja) * 2011-06-02 2012-12-20 Mitsui Chemicals Inc ポリウレタン接着剤およびラミネートフィルム
US9540513B2 (en) 2012-11-21 2017-01-10 Basf Se Lignocellulosic article and method of producing same
WO2019068529A1 (fr) * 2017-10-06 2019-04-11 Basf Se Polyisocyanates dispersibles dans l'eau
WO2021226796A1 (fr) * 2020-05-11 2021-11-18 Huntsman International Llc Composition de liant

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113103396B (zh) * 2020-01-13 2023-01-13 万华化学集团股份有限公司 一种无醛添加人造板及其制作方法
KR102515229B1 (ko) * 2023-01-26 2023-03-30 더본드 주식회사 부착성 및 유연성이 향상된 우레탄 변성 에폭시 수지 조성물 및 이를 함유하는 폴리머 박층 포장방법
KR102755619B1 (ko) * 2024-07-29 2025-01-22 시원글로벌 주식회사 도로 포장용 에폭시 포장 조성물 및 이를 이용한 저소음 배수성 포장 방법

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EP0019859A1 (fr) * 1979-05-29 1980-12-10 Bayer Ag Application de liants à base de polyisocyanates modifiés par un acide sulfonique ne collant pas au moule pour la préparation de pièces moulées
US4257995A (en) * 1979-05-03 1981-03-24 The Upjohn Company Process for preparing particle board and polyisocyanate-phosphorus compound release agent composition therefor
US4376088A (en) * 1981-03-18 1983-03-08 The Upjohn Company Process for preparing a particle board using a self-releasing binder comprising a polyisocyanate and a sulfur-containing release agent
US4382108A (en) * 1981-12-21 1983-05-03 The Upjohn Company Novel compositions and process
EP0269869A2 (fr) * 1986-11-28 1988-06-08 Jim Walter Research Corp., Composés gras contenant des groupes d'isocyanate-carboxyle pour la fabrication de composites de cellulose
US4933232A (en) * 1986-11-28 1990-06-12 Jim Walter Research Corp. Isocyanate-carboxyl group-containing fatty compounds for manufacture of lignocellulosic composites

Patent Citations (7)

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Publication number Priority date Publication date Assignee Title
US4257995A (en) * 1979-05-03 1981-03-24 The Upjohn Company Process for preparing particle board and polyisocyanate-phosphorus compound release agent composition therefor
EP0019859A1 (fr) * 1979-05-29 1980-12-10 Bayer Ag Application de liants à base de polyisocyanates modifiés par un acide sulfonique ne collant pas au moule pour la préparation de pièces moulées
US4528153A (en) * 1979-05-29 1985-07-09 Bayer Aktiengesellschaft Process for producing molded particulate articles utilizing a self-releasing binder based on a sulfonic acid modified isocyanate
US4376088A (en) * 1981-03-18 1983-03-08 The Upjohn Company Process for preparing a particle board using a self-releasing binder comprising a polyisocyanate and a sulfur-containing release agent
US4382108A (en) * 1981-12-21 1983-05-03 The Upjohn Company Novel compositions and process
EP0269869A2 (fr) * 1986-11-28 1988-06-08 Jim Walter Research Corp., Composés gras contenant des groupes d'isocyanate-carboxyle pour la fabrication de composites de cellulose
US4933232A (en) * 1986-11-28 1990-06-12 Jim Walter Research Corp. Isocyanate-carboxyl group-containing fatty compounds for manufacture of lignocellulosic composites

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998056843A1 (fr) * 1997-06-09 1998-12-17 Basf Aktiengesellschaft Emulsifiants
JP2012251063A (ja) * 2011-06-02 2012-12-20 Mitsui Chemicals Inc ポリウレタン接着剤およびラミネートフィルム
US9540513B2 (en) 2012-11-21 2017-01-10 Basf Se Lignocellulosic article and method of producing same
WO2019068529A1 (fr) * 2017-10-06 2019-04-11 Basf Se Polyisocyanates dispersibles dans l'eau
WO2021226796A1 (fr) * 2020-05-11 2021-11-18 Huntsman International Llc Composition de liant

Also Published As

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FI960997A (fi) 1996-03-04
AU2915595A (en) 1996-01-25
EP0719303A1 (fr) 1996-07-03
MY130593A (en) 2007-07-31
CN1131958A (zh) 1996-09-25
NO960868D0 (no) 1996-03-04
FI960997A0 (fi) 1996-03-04
CA2170397A1 (fr) 1996-01-18
JPH09502763A (ja) 1997-03-18
AU679645B2 (en) 1997-07-03
BR9506013A (pt) 1997-08-19
NO960868L (no) 1996-05-03
KR960704979A (ko) 1996-10-09

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